From binary AB to ternary ABC supraparticles.

Control over the assembly and morphology of nanoscale functional building blocks is of great importance to hybrid and porous nanomaterials. In this paper, by combining different types of spherical nanoparticles with different size ratios in a hierarchical assembly process which allows us to control the final structure of multi-component assemblies, we discuss self-assembly of an extensive range of supraparticles, labelled as AB particles, and an extension to novel ternary particles, labelled as ABC particles. For supraparticles, the organization of small nanoparticles is known to be inherently related to the size ratio of building blocks. Therefore, we studied the formation of supraparticles prepared by colloidal self-assembly using small silica nanoparticles (SiO ₂ NPs) attached on the surface of large polystyrene latex nanoparticles (PSL NPs) with a wide size ratio range for complete and partial coverage, by controlling the electrostatic interactions between the organic and inorganic nanoparticles and their concentrations. In this way hierarchically ordered, stable supraparticles, either fully covered or partially covered, were realized. The partially covered, stable AB supraparticles offer the option to create ABC supraparticles of which the fully covered shell contains two different types of nanoparticles. This has been experimentally confirmed using iron oxide (Fe ₃ O ₄ ) nanoparticles together with silica nanoparticles as shell particles on polystyrene core particles. Cryo-electron tomography was used to visualize the AB binary and ABC ternary supraparticles and to determine the three-dimensional structural characteristics of supraparticles formed under different conditions.